Herbicides containing 3-aryl-5-methylpyrazole-4-carboxylic acid esters, their manufacture and use

ABSTRACT

Herbicides containing a pyrazole derivative of the formula ##STR1## where R 1  denotes hydrogen, formyl, acetyl, propionyl, chloroacetyl, dichloroacetyl, methoxyacetyl, methoxycarbonyl, or phenoxycarbonyl which is unsubstituted or mono- or polysubstituted by halogen, R 2  denotes phenyl which is unsubstituted or mono- or polysubstituted by fluorine, chlorine, bromine, methyl, methoxy, cyano, nitro, trifluoromethyl, trifluoromethoxy or methoxycarbonyl, R 2  further denotes a 5- or 6-membered, heterocyclic aromatic ring which is unsubstituted or substituted by methyl or chlorine and which contains 1 or 2 hetero-atoms X, X being independently oxygen, sulfur or nitrogen, or R 2  denotes α-naphthyl or β-naphthyl, and R 3  denotes methyl, ethyl or isopropyl, or a salt of such a pyrazole derivative, a process for combating unwanted plant growth with the active ingredients and methods of manufacturing the herbicides.

This is a division of application Ser. No. 150,751 filed May 19, 1980,now abandoned.

The present invention relates to valuable herbicides containing estersof 3-aryl-5-methylpyrazole-4-carboxylic acid.

The use of 1-ethyl-3-arylpyrazole-4-carboxylic acid esters as herbicideshas been disclosed (U.S. Pat. No. 4,116,673). However, the applicationrate employed in the biological examples therein is 11.2 kg of activeingredient per hectare. In the general description of the utility of thecompounds, preferred application rates are stated to be 5.6 kg or moreof active ingredient per hectare. Particularly when the prior artcompounds are used postemergence, no special herbicidal action can beexpected. No crop plants are mentioned which do not react to the activeingredients.

We have now found that 3-aryl-5-methyl-4-alkoxycarbonylpyrazoles of theformula ##STR2## where R¹ denotes hydrogen, formyl, acetyl, propionyl,chloroacetyl, dichloroacetyl, methoxyacetyl, methoxycarbonyl, orphenoxycarbonyl which is unsubstituted or mono- or polysubstituted byhalogen, R² denotes phenyl which is unsubstituted or mono- orpolysubstituted by fluorine, chlorine, bromine, methyl, methoxy, cyano,nitro, trifluoromethyl, trifluoromethoxy or methoxycarbonyl, R² furtherdenotes a 5- or 6-membered, heterocyclic aromatic ring which isunsubstituted or substituted by methyl or chlorine and which contains 1or 2 heteroatoms X, X being independently oxygen, sulfur or nitrogen, orR² denotes α-naphthyl or β-naphthyl, and R³ denotes methyl, ethyl orisopropyl, and salts of such pyrazole derivatives, have a surprisinglystrong herbicidal action on numerous unwanted plants, especially whenused postemergence, and are acceptably tolerated by various crop plants.

The pyrazole derivatives may be in the form of salts with conventionalinorganic or organic acids, such hydrochloric acid, sulfuric acid,formic acid, methanesulfonic acid, trichloroacetic acid andp-toluenesulfonic acid. PG,3

The pyrazole derivatives are usually in isomer form (where R¹ is H, intautomer form). Where in the following it is not specifically mentionedthat only one of the two isomers is present, then the other isomer shallalso be taken to be meant by a certain formula or designation withoutthis fact having to be specifically mentioned.

In the formula of the pyrazole derivatives, R¹ denotes for instancehydrogen, formyl, acetyl, propionyl, chloroacetyl, dichloroacetyl,methoxyacetyl, methoxycarbonyl, phenoxycarbonyl, p-bromophenoxycarbonyl,2,3-dichlorophenoxycarbonyl, 3,4-dichlorophenoxycarbonyl or2,4-dichlorophenoxycarbonyl.

R² denotes for example phenyl, α-naphthyl, β-naphthyl, 2-methylphenyl,3-methylphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl,3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, 3-nitrophenyl,3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3-methoxyphenyl,3-(1,1,1-trifluoromethyloxy)-phenyl,4-(1,1,1-trifluoromethyloxy)-phenyl, 3-cyanophenyl, 2,4-dichlorophenyl,2,5-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl,2,6-difluorophenyl, 3,5-dimethylphenyl, 3-methoxycarbonylphenyl,2-methoxycarbonylphenyl, thienyl-2, thienyl-3, 4-chlorothienyl-3,furyl-2, furyl-3, 4-methyloxazolyl-5, pyridyl-2, pyridyl-3, pyridyl-4 or2,6-dichloropyridyl-4.

R³ denotes for instance methyl, ethyl or isopropyl.

The active ingredients may be manufactured for instance by any one ofthe following 5 processes:

(1) Reaction of 2-aroyl-3-methylaminocrotonic acid alkyl esters withhydrazine hydrate (Ber., 42, 3912, 1909).

(2) Reaction of 2-aroylacetoacetic acid esters with hydrazine hydrate(Ann., 279, 248, 1894).

(3) Oxidation of 3-aryl-4-alkoxycarbonyl-5-methylpyrazolines. First ofall, for example alkyl benzalacetoacetate is reacted with hydrazinehydrate, and the pyrazoline-carboxylic acid ester which is obtained isoxidized. This method of manufacture has, however, only been disclosedfor pyrazole-4-carboxylic acid ethyl esters substituted in the2-position by phenyl, which exhibit no herbicidal action. (Ber., 59,611, 1926).

(4) Addition of diazoethane to phenylpropiolic acid alkyl esters. One ofthe preferred compounds, 3-phenyl-4-methoxycarbonyl-5-methylpyrazole,was first produced by this route. (Comp. Rend., 273, Ser. C, 1772,1971).

(5) Reaction of substituted or unsubstituted thiobenzhydrazide with2-chloroacetoacetic acid alkyl esters (Ark. Kemi, 8, 537, 1955).

The preferred method of manufacture is the one given under 1). Themanufacture is described in more detail below.

SPECIFICATION 1 Manufacture of3-phenyl-4-methoxycarbonyl-5-methylpyrazole

(a) Methyl methylaminocrotonate

At 5° to 10° C., 186 g (2.4 moles) of a 40% strength aqueous methylaminesolution is dripped into a solution of 232 g (2 moles) of methylacetoacetate in 150 ml of water. The mixture is then stirred for 12hours at room temperature (20° C.). The product is then separated fromthe solution by suction filtration. After washing with ice water anddrying under reduced pressure, there is obtained 212 g (82%) of a whitesolid; m.p.: 62°-63° C.

(b) 2-Benzoyl-3-methylamino-2-butenoic acid methyl ester

193.5 g (1.5 moles) of methyl methylaminocrotonate is dissolved in 450ml of toluene, and 166.7 g (1.65 moles) of triethylamine is added; whilecooling at 0° to 5° C., 211 g (1.5 moles) (=174 ml) of benzoyl chlorideis then dripped into this mixture. After the mixture has been stirredfor 12 hours at 25° C., the precipitated triethylamine hydrochloride isfiltered off and the toluene solution is extracted with water. After thetoluene phase has been dried with Na₂ SO₄, the residue is evaporatedunder reduced pressure and the solid which is obtained is recrystallizedfrom a 4:1 mixture of ligroin and toluene. There is obtained 217 g (62%)of a white solid; m.p.: 75°-77° C.

(c) 3-Phenyl-4-methoxycarbonyl-5-methylpyrazole

At 25° to 30° C., 48.8 g (0.98 mole) of hydrazine hydrate is drippedinto a solution of 217 g (0.93 mole) of the intermediate obtained under(b) in 400 ml of glacial acetic acid. The mixture is then heated for 1hour at 100° C. After cooling to 5° C. and the addition of 600 ml ofglacial acetic acid, a white solid precipitates out which is separatedand washed with NaHCO₃ -water. Drying under reduced pressure gives 182 g(91%) of the pyrazole derivative; m.p.: 119°-120° C.

The following compounds were obtained analogously:

    ______________________________________                                         ##STR3##                                                                     No.    R.sup.1                                                                              R.sup.2        R.sup.3                                                                              m.p. (°C.)                         ______________________________________                                        1      H      phenyl         methyl 119-120                                   2      H      phenyl         ethyl  95-96                                     3      H      phenyl         isopropyl                                                                            75-77                                     4      H      α-naphthyl                                                                             methyl 142-143                                   5      H      2-methylphenyl methyl  99                                       6      H      3-methylphenyl methyl 103-105                                   7      H      2-fluorophenyl methyl 95-96                                     8      H      3-fluorophenyl methyl  96                                       9      H      4-fluorophenyl methyl 110                                       10     H      3-chlorophenyl methyl 84-85                                     11     H      4-chlorophenyl methyl 116-118                                   12     H      3-bromophenyl  methyl 63-65                                     13     H      3-nitrophenyl  methyl 185-186                                   14     H      3-CF.sub.3 -phenyl                                                                           methyl 100-103                                   15     H      4-CF.sub.3 -phenyl                                                                           methyl 104-105                                   16     H      3-methoxyphenyl                                                                              methyl 85-87                                     17     H      4-(1,1,1-trifluoro-                                                                          methyl 83-84                                                   methyloxy)-phenyl                                               18     H      3-cyanophenyl  methyl 162-164                                   19     H      2,4-dichlorophenyl                                                                           methyl 105                                       20     H      2,5-dichlorophenyl                                                                           methyl 130                                       21     H      3,4-dichlorophenyl                                                                           methyl 178-180                                   22     H      3,5-dichlorophenyl                                                                           methyl 156-158                                   23     H      2,6-difluorophenyl                                                                           methyl 114-117                                   24     H      3,5-dimethylphenyl                                                                           methyl 175                                       25     H      thienyl-2      methyl 122-124                                   26     H      thienyl-3      methyl 135-137                                   27     H      4-chlorothienyl-3                                                                            methyl 93-95                                     28     H      furyl-2        methyl 116-119                                   29     H      furyl-3        methyl 113-115                                   30     H      4-methyloxazolyl-5                                                                           methyl 133-134                                   ______________________________________                                    

If R¹ is not hydrogen, the compounds may be manufactured as follows.

SPECIFICATION 2

Manufacture of 1-acetyl-3-phenyl-4-methoxycarbonyl-5-methylpyrazole

17 g (0.08 mole) of the pyrazole derivative produced in accordance withspecification 1 is dissolved in 40 ml of acetic anhydride, and thesolution briefly boiled. After 15 minutes, the mixture is allowed tocool before being poured on to 150 g of ice. The product hascrystallized out completely after 30 minutes' stirring. The white solidis filtered off and dried under reduced pressure.

Yield: 19.6 g (95%); m.p.: 77°-78° C.

The position of the acetyl radical was inferred from spectroscopic data(nmr spectrum). It can only be definitely proved by X-ray structureanalysis.

SPECIFICATION 3 Manufacture of1-phenoxycarbonyl-3-phenyl-4-methoxycarbonyl-5-methylpyrazole

8.9 g (0.088 mole) of triethylamine is added to a solution of 17.3 g(0.08 mole) of the pyrazole derivative obtained in accordance withspecification 1 in 100 ml of tetrahydrofuran; at 15° to 20° C., 12.6 g(0.084 mole) of phenyl chloroformate is then dripped in. After themixture has been stirred for 16 hours at 25° C., the precipitatedtriethylamine hydrochloride is filtered off. The filtrate is evaporatedunder reduced pressure and the solid which remains is stirred withwater. The product is then separated from the solution by suctionfiltration and dried under reduced pressure.

Yield: 25 g (98%); m.p.: 162°-163° C.

The following compounds were obtained analogously:

    ______________________________________                                                                                m.p.                                  No.  R.sup.1         R.sup.2      R.sup.3                                                                             °C.                            ______________________________________                                        31   acetyl          phenyl       methyl                                                                              77-                                                                           78                                    32   acetyl          phenyl       ethyl 83-                                                                           86                                    33   phenoxycarbonyl phenyl       methyl                                                                              162-                                                                          163                                   34   acetyl          3-cyanophenyl                                                                              methyl                                                                              112-                                                                          115                                   35   acetyl          3-nitrophenyl                                                                              methyl                                                                              135-                                                                          137                                   36   acetyl          3-trifluoro- methyl                                                                              67-                                                        methylphenyl       68                                    37   acetyl          4-trifluoro- methyl                                                                              50-                                                        methylphenyl       53                                    38   acetyl          2-fluorophenyl                                                                             methyl                                                                              71-                                                                           74                                    39   acetyl          3-fluorophenyl                                                                             methyl                                                                              75-                                                                           78                                    40   acetyl          4-fluorophenyl                                                                             methyl                                                                              122-                                                                          123                                   41   acetyl          3-chlorophenyl                                                                             methyl                                                                              92-                                                                           94                                    42   acetyl          3-bromophenyl                                                                              methyl                                                                              79-                                                                           80                                    43   acetyl          4-chlorophenyl                                                                             methyl                                                                              109-                                                                          111                                   44   acetyl          2,5-dichloro-                                                                              methyl                                                                              80-                                                        phenyl             83                                    45   acetyl          3,4-dichloro-                                                                              methyl                                                                              132-                                                       phenyl             134                                   46   acetyl          3,5-dichloro-                                                                              methyl                                                                              130-                                                       phenyl             133                                   47   acetyl          thienyl-2    methyl                                                                              67-                                                                           69                                    48   H               2,6-dichloro-                                                                              methyl                                                                              172                                                        pyridyl-4                                                49   H               pyridyl-2    methyl                                                                              155-                                                                          158                                   50   formyl          phenyl       methyl                                      51   propionyl       phenyl       methyl                                      52   chloroacetyl    phenyl       methyl                                                                              112-                                                                          115                                   53   dichloroacetyl  phenyl       methyl                                      54   methoxyacetyl   phenyl       methyl                                                                              115-                                                                          117                                   55   methoxycarbonyl phenyl       methyl                                                                              84-                                                                           86                                    56   2-chlorophenoxy-                                                                              phenyl       methyl                                                                              117-                                       carbonyl                           118                                   57   4-chlorophenoxy-                                                                              phenyl       methyl                                                                              147                                        carbonyl                                                                 58   2,4-dichlorophen-                                                                             phenyl       methyl                                                                              115-                                       oxycarbonyl                        117                                   59   2,5-dichlorophen-                                                                             phenyl       methyl                                                                              110-                                       oxycarbonyl                        114                                   60   3,4-dichlorophen-                                                                             phenyl       methyl                                                                              130-                                       oxycarbonyl                        132                                   61   3,5-dichlorophen-                                                                             phenyl       methyl                                                                              125-                                       oxycarbonyl                        128                                   62   2,3-dichlorophen-                                                                             phenyl       methyl                                                                              140-                                       oxycarbonyl                        143                                   63   4-bromophenoxy- phenyl       methyl                                                                              154                                     64 H                                                                                              ##STR4##    methyl                                                                              110                                     65                                                                                ##STR5##       phenyl       methyl                                                                              121                                     66                                                                                ##STR6##       phenyl       methyl                                                                              145- 147                                67 acetyl          3-methylphenyl                                                                             methyl                                                                              55-                                                                           58                                      68                                                                                ##STR7##       3-Cl-phenyl  methyl                                                                              136- 139                                69                                                                                ##STR8##       3-Cl-phenyl  methyl                                                                              111- 113                              ______________________________________                                    

Application of the herbicides may be effected for instance in the formof directly sprayable solutions, powders, suspensions (includinghigh-percentage aqueous, oily or other suspensions), dispersions,emulsions, oil dispersions, pastes, dusts, broadcasting agents, orgranules by spraying, atomizing, dusting, broadcasting or watering. Theforms of application depend entirely on the purpose for which the agentsare being used; in any case they should ensure as fine a distribution ofthe above ingredient as possible.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be sprayed direct, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, further coal-tar oils, and oilsof vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons such as benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives suchas methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,etc., and strongly polar solvents such as dimethylformamide,dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions, pastes and oil dispersions the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent, adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkylsulfonates, alkali metal and alkaline earth metal salts ofdibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcoholsulfates, alkali metal and alkaline earth metal salts of fatty acids,salts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof sulfated fatty alcohol glycol ethers, condensation products ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensation products of naphthalene or naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acid, silica gels,silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground plastics, fertilizers such as ammonium sulfate,ammonium phosphate, ammonium nitrate, and ureas, and vegetable productssuch as grain flours, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 1 to 90, % byweight of active ingredient. Application rates are from 0.1 to 15 kg andmore of active ingredient per hectare, but are preferably from 0.2 to3.0 kg/ha.

The 3-aryl-5-methylpyrazole-4-carboxylic acid esters according to theinvention may be mixed with each other or mixed and applied togetherwith numerous representatives of other herbicidal or growth-regulatingactive ingredient groups. Examples of suitable mixture components arediazines, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates,biscarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides,ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives,etc. Such combinations broaden the spectrum of action, and sometimessynergistic effects are achieved.

As the herbicides are predominantly postemergence agents, they areexcellently supplemented by components which preferably act through thesoil. A number of active ingredients which, when combined with the newcompounds, give mixtures useful for widely varying applications aregiven below by way of example:

5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone

5-amino-4-bromo-2-phenyl-3(2H)-pyridazinone

5-amino-4-chloro-2-cyclohexyl-3(2H)-pyridazinone

5-amino-4-bromo-2-cyclohexyl-3(2H)-pyridazinone

5-methylamino-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone

5-methylamino-4-chloro-2-(3-,α,α,β,β-tetrafluoroethoxyphenyl)-3(2H)-pyridazinone

5-dimethylamino-4-chloro-2-phenyl-3(2H)-pyridazinone4,5-dimethoxy-2-phenyl-3(2H)-pyridazinone

4,5-dimethoxy-2-cyclohexyl-3(2H)-pyridazinone

4,5-dimethoxy-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone

5-methoxy-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone

5-amino-4-bromo-2(3-methylphenyl)-3(2H)-pyridazinone

3-(1-methylethyl)-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide andsalts

3-(1-methylethyl)-8-chloro-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxideand salts

3-(1-methylethyl)-8-fluoro-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxideand salts

3-(1-methylethyl)-8-methyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxideand salts

1-methoxymethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-methoxymethyl-8-chloro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-methoxymethyl-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-cyano-8-chloro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-cyano-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-cyano-8-methyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-cyano-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

1-azidomethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide

3-(1-methylethyl)-1H-pyridino-[3,2-e]-2,1,3-thiadiazin-(4)-one-2,2-dioxide

N-(1-ethylpropyl)-2,6-dinitro-3,4-dimethylaniline

N-(1-methylethyl)-N-ethyl-2,6-dinitro-4-trifluoromethylaniline

N-n-propyl-N-β-chloroethyl-2,6-dinitro-4-trifluoromethylaniline

N-n-propyl-N-cyclopropylmethyl-2,6-dinitro-4-trifluoromethylaniline

N-bis-(n-propyl)-2,6-dinitro-3-amino-4-trifluoromethylaniline

N-bis-(n-propyl)-2,6-dinitro-4-methylaniline

N-bis-(n-propyl)-2,6-dinitro-4-methylsulfonylaniline

N-bis-(n-propyl)-2,6-dinitro-4-aminosulfonylaniline

bis-(β-chloroethyl)-2,6-dinitro-4-methylaniline

N-ethyl-N-(2-methylallyl)-2,6-dinitro-4-trifluoromethylaniline

3,4-dichlorobenzyl N-methylcarbamate

2,6-di-tert.butyl-4-methylphenyl N-methylcarbamate

isopropyl N-phenylcarbamate

3-methoxyprop-2-yl N-3-fluorophenylcarbamate

isopropyl N-3-chlorophenylcarbamate

but-1-yn-3-yl N-3-chlorophenylcarbamate

4-chlorobut-2-yn-1-yl N-3-chlorophenylcarbamate

methyl N-3,4-dichlorophenylcarbamate

methyl N-(4-aminobenzenesulfonyl)-carbamate

O-(N-phenylcarbamoyl)-propanonoxime

N-ethyl-2-(phenylcarbamoyl)-oxypropionic acid amide

3'-N-isopropylcarbamoyloxypropionanilide

ethyl-N-(3-(N'-phenylcarbamoyloxy)-phenyl)-carbamate

methyl-N-(3-(N'-methyl-N'-phenylcarbamoyloxy)-phenyl)-carbamate

isopropyl-N-(3-(N'-ethyl-N'-phenylcarbamoyloxy)-phenyl)-carbamate

methyl-N-(3-(N'-3-methylphenylcarbamoyloxy)-phenyl)-carbamate

methyl-N-(3-(N'-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate

methyl-N-(3-(N'-3-chloro-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate

ethyl-N-[3-N'-(3-chloro-4-fluorophenylcarbamoyloxy)-phenyl]-carbamate

ethyl-N-[3-N'-(3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate

methyl-N-[3-(N'-3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate

methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylcarbamate

ethyl N-3-(2'-methylphenoxycarbonylamino)-phenylcarbamate

methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylthiolcarbamate

methyl N-3-(2',4',5'-trimethylphenoxycarbonylamino)-phenylthiolcarbamate

methyl N-3-(phenoxycarbonylamino)-phenylthiolcarbamate

p-chlorobenzyl N,N-diethylthiolcarbamate

ethyl N,N-di-n-propylthiolcarbamate

n-propyl N,N-di-n-propylthiolcarbamate

2,3-dichloroallyl N,N-diisopropylthiolcarbamate

2,3,3-trichloroalkyl N,N-diisopropylthiolcarbamate

3-methyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate

3-ethyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate

ethyl N,N-di-sec.-butylthiolcarbamate

benzyl N,N-di-sec.-butylthiolcarbamate

ethyl N-ethyl-N-cyclohexylthiolcarbamate

ethyl N-ethyl-N-bicyclo-[2.1.1]-heptylthiolcarbamate

S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate

S-(2,3,3-trichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate

S-ethylhexahydro-1-H-azepine-1-carbothiolate

S-benzyl-(3-methylhexahydro-1-H-azepine-1)-carbothiolate

S-benzyl-(2,3-dimethylhexahydro-1-H-azepine-1)-carbothiolate

S-ethyl-(3-methylhexahydro-1-H-azepine-1)-carbothiolate

n-propyl N-ethyl-N-n-butylthiolcarbamate

2-chloroallyl N,N-dimethyldithiocarbamate

N-methyldithiocarbamic acid, sodium salt

trichloroacetic acid, sodium salt

α,α-dichloropropionic acid, sodium salt

α,α-dichlorobutyric acid, sodium salt

α,α-β,β-tetrafluoropropionic acid, sodium salt

α-methyl-α,β-dichloropropionic acid, sodium salt

methyl α-chloro-β-(4-chlorophenyl)-propionate

methyl α,β-dichloro-β-phenylpropionate

benzamido oxyacetic acid

2,3,5-triiodobenzoic acid (salts, esters, amides)

2,3,6-trichlorobenzoic acid (salts, esters, amides)

2,3,5,6-tetrachlorobenzoic acid (salts, esters, amides)

2-methoxy-3,6-dichlorobenzoic acid (salts, esters, amides)

2-methoxy-3,5,6-trichlorobenzoic acid (salts, esters, amides)

3-amino-2,5,6-trichlorobenzoic acid (salts, esters, amides)

O,S-dimethyltetrachlorothioterephthalate

dimethyl-2,3,5,6-tetrachloroterephthalate

disodium-3,6-endooxohexahydrophthalate

4-amino-3,5,6-trichloropicolinic acid (salts)

ethyl 2-cyano-3-(N-methyl-N-phenyl)-aminoacrylate

isobutyl 2-[4-(4'-chlorophenoxy)-phenoxy]-propionate

methyl 2-[4-(2',4'-dichlorophenoxy)-phenoxy]-propionate

methyl 2-[4-(4'-trifluoromethylphenoxy)-phenoxy]-propionate

2-[4-(2'-chloro-4'-trifluorophenoxy)-phenoxy]-propionic acid, sodiumsalt

2-[4-(3',5'-dichloropyridyl-2-oxy)-phenoxy]-propionic acid, sodium salt

ethyl 2-(N-benzoyl-3,4-dichlorophenylamino)-propionate

methyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate

isopropyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate

2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine

2-chloro-4-ethylamino-6-(amino-2'-propionitrile)-1,3,5-triazine

2-chloro-4-ethylamino-6-(2-methoxypropyl)-2-amino-1,3,5-triazine

2-chloro-4-ethylamino-6-butyn-1-yl-2-amino-1,3,5-triazine

2-chloro-4,6-bisethylamino-1,3,5-triazine

2-chloro-4,6-bisisopropylamino-1,3,5-triazine

2-chloro-4-isopropylamino-6-cyclopropylamino-1,3,5-triazine

2-azido-4-methylamino-6-isopropylamino-1,3,5-triazine

2-methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine

2-methylthio-4-ethylamino-6-tert.butylamino-1,3,5-triazine

2-methylthio-4,6-bisethylamino-1,3,5-triazine

2-methylthio-4,6-bisisopropylamino-1,3,5-triazine

2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine

2-methoxy-4,6-bisethylamino-1,3,5-triazine

2-methoxy-4,6-bisisopropylamino-1,3,5-triazine

4-amino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one

4-amino-6-phenyl-3-methyl-4,5-dihydro-1,2,4-triazin-5-one

4-isobutylidenamino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one

1-methyl-3-cyclohexyl-6-dimethylamino-1,3,5-triazine-2,4-dione

3-tert.butyl-5-chloro-6-methyluracil

3-tert.butyl-5-bromo-6-methyluracil

3-isopropyl-5-bromo-6-methyluracil

3-sec.butyl-5-bromo-6-methyluracil

3-(2-tetrahydropyranyl)-5-chloro-6-methyluracil

3-(2-tetrahydropyranyl)-5,6-trimethyleneuracil

3-cyclohexyl-5,6-trimethyleneuracil

2-methyl-4-(3'-trifluoromethylphenyl)-tetrahydro-1,2,4-oxadiazine-3,5-dione

2-methyl-4-(4'-fluorophenyl)-tetrahydro-1,2,4-oxadiazine-3,5-dione3-amino-1,2,4-triazole

1-allyloxy-1-(4-bromophenyl)-2-[1',2',4'-triazolyl-(1')]-ethane (salts)

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,3-triazol-1-yl)-butan-2-one

N,N-diallylchloroacetamide

N-isopropyl-2-chloroacetanilide

N-(but-1-yn-3-yl)-2-chloroacetanilide

2-methyl-6-ethyl-N-propargyl-2-chloroacetanilide

2-methyl-6-ethyl-N-ethoxymethyl-2-chloroacetanilide

2-methyl-6-ethyl-N-(2-methoxy-1-methylethyl)-2-chloroacetanilide

2-methyl-6-ethyl-N-(isopropoxycarbonylethyl)-2-chloroacetanilide

2-methyl-6-ethyl-N-(4-methoxypyrazol-1-yl-methyl)-2-chloroacetanilide

2-methyl-6-ethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(4-methylpyrazol-1-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(1,2,4-triazol-1-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(1,3-dioxolan-2-yl-methyl)-2-chloroacetanilide

2,6-dimethyl-N-(2-methoxyethyl)-2-chloroacetanilide

2,6-dimethyl-n-isobutoxymethyl-2-chloroacetanilide

2,6-diethyl-n-methoxymethyl-2-chloroacetanilide

2,6-diethyl-N-n-butoxymethyl-2-chloroacetanilide

2,6-diethyl-N-ethoxycarbonylmethyl-2-chloroacetanilide

2,3,6-trimethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide

2,3-dimethyl-N-isopropyl-2-chloroacetanilide

2,6-dimethyl-N-(propoxyethyl)-2-chloroacetanilide

2-(2-methyl-4-chlorophenoxy-N-methoxyacetamide

2-(α-naphthoxy)-N,N-diethylpropionamide

2,2-diphenyl-N,N-dimethylacetamide

α-(3,4,5-tribromopyrazol-1-yl)-N,N-dimethylpropionamide

N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide

N-1-naphthylphthalamic acid

propionic acid-3,4-dichloroanilide

cyclopropanecarboxylic acid-3,4-dichloroanilide

methacrylic acid-3,4-dichloroanilide

2-methylpentanecarboxylic acid-3,4-dichloroanilide

N-2,4-dimethyl-5-(trifluoromethyl)-sulfonylaminophenylacetamide

N-4-methyl-5-(trifluoromethyl)-sulfonylaminophenylacetamide

2-propionylamino-4-methyl-5-chlorothiazole

O-(methylsulfonyl)-glycolic acid-N-ethoxymethyl-2,6-dimethylanilide

O-(methylaminosulfonyl)-glycolic acid-N-isopropylanilide

O-(isopropylaminosulfonyl)-glycolic acid-N-but-1-yn-3-yl-anilide

O-(methylaminosulfonyl)-glycolic acid hexamethyleneamide

2,6-dichlorothiobenzamide

2,6-dichlorobenzonitrile

3,5-dibromo-4-hydroxybenzonitrile (salts)

3,5-diiodo-4-hydroxybenzonitrile (salts)

3,5-dibromo-4-hydroxy-O-2.4-dinitrophenylbenzaldoxime (salts)

3,5-dibromo-4-hydroxy-O-2-cyano-4-nitrophenylbenzaldoxime (salts)

pentachlorophenol, sodium salt

2,4-dichlorophenyl-4'-nitrophenyl ether

2,4,6-trichlorophenyl-4'-nitrophenyl ether

2-fluoro-4,6-dichlorophenyl-4'-nitrophenyl ether

2-chloro-4-trifluoromethylphenyl-4'-nitrophenyl ether

2,4'-dinitro-4-trifluoromethyl-diphenyl ether

2,4-dichlorophenyl-3'-methoxy-4'-nitro-phenyl ether

2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-nitro-phenyl ether

2-chloro-4-trifluoromethylphenyl-3'-carboxy-4'-nitro-phenyl ether(salts)

2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitro-phenyl ether

2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione

2-(3-tert.butylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione

2-(3-isopropylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione

2-phenyl-3,1-benzoxazinone-(4)

(4-bromophenyl)-3,4,5,9,10-pentaazatetracyclo-[5,4,1,0²,6, O,⁸,11]-dodeca-3,9-diene

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylmethane sulfonate

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyldimethylaminosulfate

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-(N-methyl-N-acetyl)-aminosulfonate

3,4-dichloro-1,2-benzisothiazole

N-4-chlorophenyl-allylsuccinimide

2-methyl-4,6-dinitrophenol (salts, esters)

2-sec.butyl-4,6-dinitrophenol (salts, esters)

2-sec.butyl-4,6-dinitrophenol acetate

2-tert.butyl-4,6-dinitrophenol acetate

2-tert.butyl-4,6-dinitrophenol (salts)

2-tert.butyl-5-methyl-4,6-dinitrophenol (salts)

2-tert.butyl-5-methyl-4,6-dinitrophenol acetate

2-sec.amyl-4,6-dinitrophenol (salts, esters)

1-(α,α-dimethylbenzyl)-3-(4-methylphenyl)-urea

1-phenyl-3-(2-methylcyclohexyl)-urea

1-phenyl-1-benzoyl-3,3-dimethylurea

1-(4-chlorophenyl)-1-benzoyl-3,3-dimethylurea

1-(4-chlorophenyl)-3,3-dimethylurea

1-(4-chlorophenyl)-3-methyl-3-but-1-yn-3-yl-urea

1-(3,4-dichlorophenyl)-3,3-dimethylurea

1-(3,4-dichlorophenyl)-1-benzoyl-3,3-dimethylurea

1-(3,4-dichlorophenyl)-3-methyl-3-n.butylurea

1-(4-isopropylphenyl)-3,3-dimethylurea

1-(3-trifluoromethylphenyl)-3,3-dimethylurea

1-(α,α,β,β-tetrafluoroethoxyphenyl)-3,3-dimethylurea

1-(3-tert.butylcarbamoyloxyphenyl)-3,3-dimethylurea

1-(3-chloro-4-methylphenyl)-3,3-dimethylurea

1-(3-chloro-4-methoxyphenyl)-3,3-dimethylurea

1-(3,5-dichloro-4-methoxyphenyl)-3,3-dimethylurea

1-[4-(4'-chlorophenoxy)-phenyl]-3,3-dimethylurea

1-[4-(4'-methoxyphenoxy)-phenyl]-3,3-dimethylurea

1-cyclooctyl-3,3-dimethylurea

1-(hexahydro-4,7-methanoindan-5-yl)-3,3-dimethylurea

1-[1- or 2-(3a,4,5,7,7a-hexahydro)-4,7-methanoindanyl]-3,3-dimethylurea

1-(4-fluorophenyl)-3-carboxymethoxy-3-methylurea

1-phenyl-3-methyl-3-methoxyurea

1-(4-chlorophenyl)-3-methyl-3-methoxyurea

1-(4-bromophenyl)-3-methyl-3-methoxyurea

1-(3,4-dichlorophenyl)-3-methyl-3-methoxyurea

1-(3-chloro-4-bromophenyl)-3-methyl-3-methoxyurea

1-(3-chloro-4-isopropylphenyl)-3-methyl-3-methoxyurea

1-(3-chloro-4-methoxyphenyl)-3-methyl-3-methoxyurea

1-(3-tert.butylphenyl)-3-methyl-3-methoxyurea

1-(2-benzthiazolyl)-1,3-dimethylurea

1-(2-benzthiazolyl)-3-methylurea

1-(5-trifluoromethyl-1,3,4-thiadiazolyl)-1,3-dimethylurea

imidazolidin-2-one-1-carboxylic acid isobutylamide

1,2-dimethyl-3,5-diphenylpyrazolium-methylsulfate

1,2,4-trimethyl-3,5-diphenylpyrazolium-methylsulfate

1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium-methylsulfate

1,3-dimethyl-4-(3,4-dichlorobenzoyl)-5-(4-methylphenylsulfonyloxy)-pyrazole

2,3,5-trichloropyridinol-(4)

1-methyl-3-phenyl-5-(3'-trifluoromethylphenyl)-pyridone-(4)

1-methyl-4-phenylpyridinium chloride

1,1-dimethylpyridinium chloride

3-phenyl-4-hydroxy-6-chloropyridazine

1,1'-dimethyl-4,4'-dipyridylium-di(methylsulfate)

1,1'-di-(3,4-dimethylmorpholine-carbonylmethyl)-4,4'-dipyridyliumdichloride

1,1'-ethylene-2,2'-dipyridylium dibromide

3-[1-(N-ethoxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

3-[1-(N-allyloxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

2-[1-(N-allyloxyamino)-propylidene]-5,5-dimethylcyclohexane-1,3-dione(salts)

2-[1-(N-allyloxyamino-butylidene]-5,5-dimethylcyclohexane-1,3-dione(salts)

2-[1-(N-allyloxyamino-butylidene]-5,5-dimethyl-4-methoxycarbonyl-cyclohexane-1,3-dione(salts)

2-chlorophenoxyacetic acid (salts, esters, amides)

4-chlorophenoxyacetic acid (salts, esters, amides)

2,4-dichlorophenoxyacetic acid (salts, esters, amides)

2,4,5-trichlorophenoxyacetic acid (salts, esters, amides)

2-methyl-4-chlorophenoxyacetic acid (salts, esters, amides)

3,5,6-trichloro-2-pyridinyl-oxyacetic acid (salts, esters, amides)

methyl α-naphthoxyacetate

2-(2-methylphenoxy)-propionic acid (salts, esters, amides)

2-(4-chlorophenoxy)-propionic acid (salts, esters, amides)

2-(2,4-dichlorophenoxy)-propionic acid (salts, esters, amides)

2-(2,4,5-trichlorophenoxy)-propionic acid (salts, esters, amides)

2-(2-methyl-4-chlorophenoxy)-propionic acid (salts, esters, amides)

4-(2,4-dichlorophenoxy)-butyric acid (salts, esters, amides)

4-(2-methyl-4-chlorophenoxy)-butyric acid (salts, esters, amides)

cyclohexyl-3-(2,4-dichlorophenoxy)-acrylate

9-hydroxyfluorenecarboxylic acid-(9) (salts, esters)

2,3,6-trichlorophenylacetic acid (salts, esters)

4-chloro-2-oxobenzothiazolin-3-yl-acetic acid (salts, esters)

gibelleric acid (salts)

disodium methylarsonate

monosodium salt of methylarsonic acid

N-phosphonomethyl-glycine (salts)

N,N-bis-(phosphonomethyl)-glycine (salts)

2-chloroethyl 2-chloroethanephosphonate

ammonium-ethyl-carbamoyl-phosphonate

di-n-butyl-1-n-butylamino-cyclohexyl-phosphonate

trithiobutylphosphite

O,O-diisopropyl-5-(2-benzosulfonylaminoethyl)-phosphorodithionate

2,3-dihydro-5,6-dimethyl-1,4-dithiin-1,1,4,4-tetraoxide

5-tert.butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazolone-(2)

4,5-dichloro-2-trifluoromethylbenzimidazole (salts)

1,2,3,6-tetrahydropyridazine-3,6-dione (salts)

succinic acid mono-N-dimethylhydrazide (salts)

(2-chloroethyl)-trimethylammonium chloride

(2-methyl-4-phenylsulfonyl)-trifluoromethanesulfone anilide

1,1-dimethyl-4,6-diisopropyl-5-indanyl ethyl ketone

sodium chlorate

ammonium thiocyanate

calcium cyanamide

2-chloro-4-trifluoromethyl-3'-ethoxycarbonyl-4'-nitrophenyl ether

1-(4-benzyloxyphenyl)-3-methyl-3-methoxyurea

2-[1-(2,5-dimethylphenyl)-ethylsulfonyl]-pyridine-N-oxide.

It may also be useful to apply the active ingredients, either alone orin combination with other herbicides, in admixture with other cropprotection agents, e.g., agents for combating pests or phytopathogenicfungi or bacteria. The compounds may also be mixed with solutions ofmineral matters used to remedy nutritional or trace elementdeficiencies. To initiate the herbicidal action, wetting agents,spreader-stickers and non-phytotoxic oils and oil concentrates may beadded.

The following greenhouse experiments demonstrate the influence ofvarious herbicides on the growth of crop and unwanted plants.

The vessels employed were plastic flowerpots having a volume of 300 cm³,and which were filled with a sandy loam containing about 1.5% humus. Theseeds of the test plants (cf. Table 1) were sown shallow, andseparately, according to species. For the postemergence treatment, theplants were grown to a height of from 3 to 10 cm. Certain test plantspecies were first grown as seedlings in special seedling vessels beforebeing transplanted to the plastic pots described above. The chemicalagents were then applied a few days after the plants had taken root. Theactive ingredients were suspended or emulsified in water as vehicle andsprayed onto the plants through finely distributing nozzles. The potswere then set up in the greenhouse--species from warmer areas at from25° to 40° C., and species from moderate climates at from 15° to 30° C.The experiments were run for from 3 to 6 weeks. During this period, theplants were tended and their reactions to the various treatmentsassessed. The following tables containing the compounds investigated,the application rates in kg/ha of active ingredient, and the plants usedfor the tests. The scale used for assessment was 0 to 100, 0 denoting nodamage or normal emergence, and 100 denoting nonemergence or completedestruction of at least the visible plant parts.

The selective herbicidal action of the active ingredients isdemonstrated in the following tables. The compounds are predominantlyapplied postemergence, but they also have an effect when appliedpreemergence. A special application technique consists in spraying theactive ingredients with spray equipment in such a manner that the leavesof sensitive crop plants are if possible not contacted, and the activeingredients reach the soil or the unwanted plants growing there(post-directed, lay-by). In addition to the unwanted plants listed inthe tables, the wild oat species Avena fatua and Avena ludoviciana,slender foxtail (Alopecurus myosuroides) and numerous other unwantedgrasses and weeds are combated.

In view of the wide variety of application methods, the herbicides, ormixtures containing them, may be used to combat unwanted plant growth ina large number of crops.

The following crop plants may be mentioned as examples:

    ______________________________________                                        Botanical name    Common name                                                 ______________________________________                                        Allium cepa       onions                                                      Ananas comosus    pineapples                                                  Arachis hypogaea  peanuts (groundnuts)                                        Asparagus officinalis                                                                           asparagus                                                   Avena sativa      oats                                                        Beta vulgaris spp. altissima                                                                    sugarbeets                                                  Beta vulgaris spp. rapa                                                                         fodder beets                                                Beta vulgaris spp. esculenta                                                                    table beets, red beets                                      Brassica napus var. napus                                                                       rape                                                        Brassica napus var. napobrassica                                              Brassica napus var. rapa                                                                        turnips                                                     Brassica rapa var. silvestris                                                 Camellia sinensis tea plants                                                  Carthamus tinctorius                                                                            safflower                                                   Carya illinoinensis                                                                             pecan trees                                                 Citrus limon      lemons                                                      Citrus maxima     grapefruits                                                 Citrus reticulata                                                             Citrus sinensis   orange trees                                                Coffea arabica (Coffea canephora,                                                               coffee plants                                               Coffea liberica)                                                              Cucumis melo      melons                                                      Cucumis sativus   cucumbers                                                   Cynodon dactylon  Bermudagrass in turf and                                                      lawns                                                       Daucus carota     carrots                                                     Elais guineensis  oil palms                                                   Fragaria vesca    strawberries                                                Glycine max       soybeans                                                    Gossypium hirsutum                                                                              cotton                                                      (Gossypium arboreum                                                           Gossypium herbaceum                                                           Gossypium vitifolium)                                                         Helianthus annuus sunflowers                                                  Helianthus tuberosus                                                          Hevea brasiliensis                                                                              rubber plants                                               Hordeum vulgare   barley                                                      Humulus lupulus   hops                                                        Ipomoea batatas   sweet potatoes                                              Juglans regia     walnut trees                                                Lactuca sativa    lettuce                                                     Lens culinaris    lentils                                                     Linum usitatissimum                                                                             flax                                                        Lycopersicon lycopersicum                                                                       tomatoes                                                    Malus spp.        apple trees                                                 Manihot esculenta cassava                                                     Medicago sativa   alfalfa (lucerne)                                           Mentha piperita   peppermint                                                  Musa spp.         banana plants                                               Nicothiana tabacum                                                                              tobacco                                                     (N. rustica)                                                                  Olea europaea     olive trees                                                 Oryza sativa      rice                                                        Panicum miliaceum                                                             Phaseolus lunatus limabeans                                                   Phaseolus mungo   mungbeans                                                   Phaseolus vulgaris                                                                              snapbeans, green beans,                                                       dry beans                                                   Pennisetum glaucum                                                            Petroselinum crispum                                                                            parsley                                                     spp. tuberosum                                                                Picea abies       Norway spruce                                               Abies alba        fir trees                                                   Pinus spp.        pine trees                                                  Pisum sativum     English peas                                                Prunus avium      cherry trees                                                Prunus domestica  plum trees                                                  Prunus dulcis     almond trees                                                Prunus persica    peach trees                                                 Pyrus communis    pear trees                                                  Ribes sylvestre   redcurrants                                                 Ribes uva-crispa                                                              Ricinus communis                                                              Saccharum officinarum                                                                           sugar cane                                                  Secale cereale    rye                                                         Sesamum indicum   sesame                                                      Solanum tuberosum Irish potatoes                                              Sorghum bicolor (s. vulgare)                                                                    grain sorghum                                               Sorghum dochna                                                                Spinacia oleracea spinach                                                     Theobroma cacao   cacao plants                                                Trifolium pratense                                                                              red clover                                                  Triticum aestivum wheat                                                       Vaccinium corymbosum                                                                            blueberries                                                 Vaccinium vitis-idaea                                                                           cranberries                                                 Vicia faba        tick beans                                                  Vigna sinensis (V. unguiculata)                                                                 cow peas                                                    Vitis vinifera    grapes                                                      Zea mays          Indian corn, sweet corn, maize                              ______________________________________                                    

                  TABLE 1                                                         ______________________________________                                        List of plants used in the experiments                                                     Abbreviation                                                     Botanical name                                                                             in tables    Common name                                         ______________________________________                                        Amaranthus retroflexus                                                                     Amar. retr.  redroot pigweed                                     Arachis hypogaea                                                                           Arachis hyp. peanuts (ground nuts)                               Datura stramonium                                                                          Datura stram.                                                                              jimsonweed                                          Echinochloa crus galli                                                                     Echinochl. c.g.                                                                            barnyardgrass                                       Hordeum vulgare                                                                            Hordeum vulg.                                                                              barley                                              Ipomoea spp.              morningglory                                        Lamium amplexicaule                                                                        Lamium amplexic.                                                                           henbit                                              Nicandra physaloides                                                                       Nicandra phys.                                                                             apple-of-Peru                                       Rumex optusifolius                                                                         Rumex otus.  broadleaf dock                                      Sesbania exaltata                                                                          Sesbania exalt.                                                                            hemp sesbania                                                                 (coffee weed)                                       Sorghum bicolor           sorghum                                             Sorghum halepense                                                                          Sorghum halep.                                                                             Johnsongrass                                        Sinapis alba              white mustard                                       Triticum aestivum                                                                          Tritic. aest.                                                                              wheat                                               Solanum nigrum            black nightshade                                    ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Selective control of broadleaved weeds in wheat;                              postemergence application in the greenhouse                                                Test plants and % damage                                         Compound           Tritic. Lamium Sinapis                                                                             Solanum                               no.        kg/ha   aest.   amplexic.                                                                            alba  nigrum                                ______________________________________                                        5          0.5     10       80    95    100                                   22         0.25    0       100    95    100                                   28         0.5     0        90    --    --                                    6          0.25    0       100    95    100                                   8          0.25    10      100    95    100                                   12         0.25    10      100    90    100                                   7          0.25    0       100    90    100                                   9          0.25    10      100    90    100                                   16         0.25    10      100    90    --                                    18         0.5     0       100    85    100                                   42         0.25    0       100    95    100                                   35         1.0     0       100    95    100                                   38         0.5     0       100    90    100                                   39         0.25    10      100    95    100                                   40         0.25    0       --     90    100                                   46         0.25    0       100    95    100                                   41         0.25    0       100    95    100                                   47         0.25    0       100    90    100                                   48         1.0     10      100    --    100                                   (U.S. Pat. No.                                                                           2.0     10       20    20     40                                   4,116,673)                                                                    A = 1-methyl-3-[3'-trifluoromethylphenyl]-4-methoxycarbonyl-                  pyrazole                                                                      (U.S. Pat. No.                                                                           2.0      0      40     20     30                                   4,116,673)                                                                    B = 1-methyl-3-phenyl-4-ethoxycarbonylpyrazole                                ______________________________________                                         0 = no damage                                                                 100 = plants destroyed                                                   

                  TABLE 3                                                         ______________________________________                                        Control of unwanted broadleaved plants in sorghum;                            postemergence treatment in the greenhouse                                     Com-          Test plants and % damage                                        pound         Sorghum  Amar. Datura                                                                              Nicandra                                                                             Sesbania                            no.   kg/ha   bicolor  retr. stram.                                                                              phys.  exalt.                              ______________________________________                                         6    0.25    10        80    98   100    100                                 14    1.0     10       100   100   100    100                                 33    1.0     5         70   100   100    100                                 34    2.0     10       100   100   100    100                                  8    0.5     0        100   100   100     98                                 41    0.5     0        100   100   100    100                                 47    1.0     5        100   100   100    100                                  1    0.5     5         70   100   100    100                                  7    0.5     0        --     98   100    100                                 42    0.5     10       100   100   100    100                                 40    1.0     10       100   100   100    100                                 46    1.0     10       100   100   100    100                                 A     2.0     5         0     10    20     90                                 B     2.0     15        0     30    40     10                                 ______________________________________                                         0 = no damage                                                                 100 = plants destroyed                                                   

                  TABLE 4                                                         ______________________________________                                        Control of unwanted plant growth in groundnuts;                               postemergence treatment in the greenhouse                                               Test plants and % damage                                                                          Echin-                                                                              Impo-                                     Compound        Arachis Amar. ochl. moea  Sorghum                             no.     kg/ha   hyp.    retr. c.g.  spp.  halep.                              ______________________________________                                        31      2.0     5       100   100   95    85                                  10      1.0     10      100   95    95    95                                  25      1.0     10      100   90    80    90                                  36      2.0     10       60   94    100   88                                   9      1.0     0        45   90    80    95                                  39      1.0     0       100   95    100   85                                  41      1.0     5       100   98    100   90                                  47      1.0     5       100   80    90    85                                   6      2.0     0       100   98    100   80                                  16      2.0     0        60   100   60    100                                 42      2.0     0       100   90    70    98                                  A       2.0     0        0     0     0     0                                  (U.S.   2.0     0        0     0     0     0                                  Pat. No. -4,116,673)                                                          C = 1-methyl-3-[3'-trifluoromethylphenyl]-4-ethoxycarbonyl-                   pyrazole                                                                      ______________________________________                                         0 = no damage                                                                 100 =  plants destroyed                                                  

                  TABLE 5                                                         ______________________________________                                        Herbicidal action on Ipomoea spp.; postemerrgence                             treatment in the greenhouse                                                   Compound               Damage (%) to                                          no.            kg/ha   Ipomoea spp.                                           ______________________________________                                        15             3.0     100                                                    24             3.0     100                                                    32             3.0     100                                                    37             3.0     100                                                    43             3.0     100                                                    44             3.0     100                                                    45             3.0     100                                                    26             3.0      90                                                    29             3.0     100                                                    52             3.0     100                                                    54             3.0     100                                                    55             3.0     100                                                    ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        Selective control of unwanted plants in cereals; postemergence                treatment in the greenhouse                                                            Test plants and % damage                                             Compound                                                                              kg/    Hordeum  Tritic.                                                                             Lamium Rumex Sinapis                            no.     ha     vulg.    aest. amplex.                                                                              obtus.                                                                              alba                               ______________________________________                                        2       0.5    0        0     80     90    95                                 B       0.5    0        0     30      0    10                                 ______________________________________                                    

EXAMPLE 1

90 parts by weight of compound 1 is mixed with 10 parts by weight ofN-methyl-α-pyrrolidone. A mixture is obtained which is suitable forapplication in the form of very fine drops.

EXAMPLE 2

20 parts by weight of compound 2 is dissolved in a mixture consisting of80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide,5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid,and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1mole of castor oil. By pouring the solution into 100,000 parts by weightof water and uniformly distributing it therein, an aqueous dispersion isobtained containing 0.02% by weight of the active ingredient.

EXAMPLE 3

20 parts by weight of compound 3 is dissolved in a mixture consisting of40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol,20 parts by weight of the adduct of 7 moles of ethylene oxide with 1mole of isooctylphenol, and 10 parts by weight of the adduct of 40 molesof ethylene oxide with 1 mole of castor oil. By pouring the solutioninto 100,000 parts by weight of water and finely distributing ittherein, an aqueous dispersion is obtained containing 0.02% by weight ofthe active ingredient.

EXAMPLE 4

20 parts by weight of compound 1 is dissolved in a mixture consisting of25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oilfraction having a boiling point between 210° and 280° C., and 10 partsby weight of the adduct of 40 moles of ethylene oxide with 1 mole ofcastor oil. By pouring the solution into 100,000 parts by weight ofwater and uniformly distributing it therein, an aqueous dispersion isobtained containing 0.02% by weight of the active ingredient.

EXAMPLE 5

20 parts by weight of compound 3 is well mixed with 3 parts by weight ofthe sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts byweight of the sodium salt of a lignin-sulfonic acid obtained from asulfite waste liquor, and 60 parts by weight of powdered silica gel, andtriturated in a hammer mill. By uniformly distributing the mixture in20,000 parts by weight of water, a spray liquor is obtained containing0.1% by weight of the active ingredient.

EXAMPLE 6

3 parts by weight of compound 3 is intimately mixed with 97 parts byweight of particulate kaolin. A dust is obtained containing 3% by weightof the active ingredient.

EXAMPLE 7

30 parts by weight of compound 4 is intimately mixed with a mixtureconsisting of 92 parts by weight of powdered silica gel and 8 parts byweight of paraffin oil which has been sprayed onto the surface of thissilica gel. A formulation of the active ingredient is obtained havinggood adherence.

EXAMPLE 8

40 parts by weight of compound 1 is intimately mixed with 10 parts ofthe sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2parts of silica gel and 48 parts of water. Dilution in 100,000 parts byweight of water gives an aqueous dispersion containing 0.04 wt% ofactive ingredient.

EXAMPLE 9

20 parts of compound 2 is intimately mixed with 2 parts of the calciumsalt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcoholpolyglycol ether, 2 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate and 68 parts of a paraffinic mineraloil. A stable oily dispersion is obtained.

We claim:
 1. A process for combating the growth of unwanted plants,wherein the plants are treated with a herbicidally effective amount of apyrazole derivative of the formula ##STR9## where R¹ denotes hydrogen,R² denotes phenyl which is unsubstituted or mono-substituted byfluorine, chlorine, bormine, methyl methoxy, cyano trifluoromethyl,trifluoromethoxy or methoxycarbonyl, R² further denotes, anunsubstituted or methyl- or chloro-substituted thienyl, furyl, oxazolylor pyridyl, or R² denotes α-naphthyl or β-naphthyl, and R³ denotesmethyl, or a salt thereof.